No.

266/1 e

Application Bulletin
Of interest to:

General analytical laboratories, Waters, Metals Energy, Environmental protection, Trace analysis

B 1, 2, 6, 9, 10, 15, 16

Determination of titanium and uranium by voltammetry

Summary
This bulletin describes extremely sensitive methods for the determination of titanium and uranium. They are especially suitable for the analysis of ground, drinking, sea, surface and cooling waters, in which the concentration of these elements is of importance. The methods can, of course, also be used for the trace analysis in other matrices. Titanium is determined by adsorptive stripping voltammetry (AdSV) with mandelic acid as complexing agent. The determination limit lies at 0.5 g/L. Also uranium is determined as chloranilic acid complex with adsorptive stripping voltammetry. Here the determination limit lies in low-chloride media at 50 ng/L, in seawater at 1 g/L and in high-chloride media in a ppm range, after the chloride has been removed by means of a sulphate-loaded ion exchanger.

Apparatus and accessories

746 VA Trace Analyzer with 747 VA Stand or 757 VA Computrace

Sample preparation
Organic matter often interferes with voltammetric determinations and therefore sample solutions usually have to be digested. Ground water, surface waters, mineral waters and drinking waters can usually be analysed without pre-treatment. Low polluted waste waters can be digested with the 705 UV-Digester. Add 50 - 100 L w(H2O2) = 30% and 10 L w(HCl) = 30% to 10 mL acidified sample (pH = 2) and irradiate for 1h at 90C. After cooling to room temperature, the digested sample can be transferred directly to the polarographic vessel. Samples with organic matter (foods, pharmaceuticals etc.) must be digested. - High-pressure asher - Microwave digestion Both techniques oxidise the sample in a closed digestion vessel by means of a mixture of concentrated mineral acids. - According to AB 113, open wet digestion with H2SO4 and H2O2

Application Bulletin Determination of titanium and uranium by voltammetry Literature

No. 266/1 e Page 2

Henze G., Sander S. Adsorption voltammetric techniques for the determination of uranium(VI) with 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone as complex forming reagent Fresenius J Anal Chem (1994) 349:654-658 Henze G., Sander S., Wagner W. Direct Determination of Uranium Traces by Adsorptive Stripping Voltammetry Universitten Kaiserslautern und Trier 1994 Henze G., Sander S. Chloranilsure als Komplexbildner fr die Ultraspurenanalyse von Elementen durch Adsorptions-Stripping-Voltammetrie GIT Fachz. Lab. 12/96 Van den Berg, C.M.G. Potentials and potentialities of cathodic stripping voltammerty of trace elements in natural waters. Anal. Chim. Acta (1991) 250: 265-276 Yokoi, K. Van den Berg, C.M.G. Determination of titanium in sea water using catalytic cathodic stripping voltammetry Anal. Chim. Acta (1991) 245: 2/ 167-176 Li, H., Van den Berg, C.M.G. Determination of Titanium in sea water using adsorptive cathodic stripping voltammetry Anal. Chim. Acta (1989) 221/2 269-277 Metrohm Application Bulletin 113

Application Bulletin Determination of titanium and uranium by voltammetry

No. 266/1 e Page 3

Method 1 Titanium determination

Theory
Titanium forms a complex with mandelic acid which can be determined by adsorptive stripping voltammetry.

Reagents
All of the used reagents must be of purest quality possible (analytical grade or suprapur). Only ultrapure water should be used. DL-mandelic acid, puriss p.a., CAS 611-72-3 Ammonia solution, suprapur, w(NH3) = 25 % Ti standard stock solution, (Ti) = 1 g/L (commercially available) Ready-to-use solutions Mandelic acid solution: c(mandelic acid) = 0.4 mol/L 6.1 g mandelic acid are dissolved in 100 mL ultrapure water. The solution is stable for 1 week. diluted ammonia solution: w(NH3) = 10% The ammonia solution is diluted with ultrapure water as appropriate. Ti Standard 1mg/L: The standard stock solution is diluted with c(HCl) = 0.1 mol/L. The standard has to be prepared anew daily.

Analysis
Measuring solution 10 mL (diluted) sample + 1 mL mandelic acid solution Adjust the pH value to 3.0 with w(NH3) = 10 %. The voltammogram is recorded with the following parameters: Working electrode Stirrer/RDE Drop size Measurement mode Purge time Pulse amplitude Deposition potential Deposition time Equilibration time Start potential End potential Voltage step Voltage step time Sweep rate Peak potential (Ti) HMDE 2000 rpm 4 DP 300 s 0.05 V - 0.57 V 30 s 5s - 0.57 V - 0.95 V 0.004 V 0.2 s 0.02 V/s - 0.79 V

The concentration is determined by standard addition.

Application Bulletin Determination of titanium and uranium by voltammetry Figures

-14.0n

No. 266/1 e Page 4

Ti
-12.0n

Ti c = +/-

1.353 g/L 0.035 g/L (2.55%)

-6.00n

-10.0n

I (A)

-8.00n

-6.00n
-2.00n

-4.00n

I (A)

-4.00n

-2.00n -0.65 -0.70 -0.75 -0.80 -0.85 -0.90

-1.4e-006
0 -1.00u 0 1.00u 2.00u

U (V)

c / (g/L)

==================== METROHM 757 VA COMPUTRACE (5.757.0020) ==================== Determ. : 11021144_Sea Water Ti.dth Sample ID : Sea Water Ti Creator : --Date : 1999-11-02 Time: 11:44:42 Modified by : zu Date : 2001-07-05 Time: 08:43:10 User : zu Date : 2001-07-05 Time: 08:43:11 -------------------------------------------------------------------------------Cell volume: 11.000 mL Sample amount: 10.000 mL -------------------------------------------------------------------------------Method : Ti Determination.mth Title : Ti i n Sea Water Remark1 : 10 mL Seawater + 1mL Mandelic Acid 0.4 mol/L Remark2 : NH3 10% --->pH 3 -------------------------------------------------------------------------------Substance : Ti Comments Mass conc.: 1.230 ug/L -----------------MC.dev. : 0.031 ug/L ( 2.55%) Mass : 13.534 ng Add.mass : 10.000 ng VR ---1-1 1-2 2-1 2-2 3-1 3-2 Substance --------Ti V -----0.788 -0.788 -0.788 -0.788 -0.788 -0.788 nA ------2.785 -2.863 -4.916 -4.992 -7.024 -6.982 I.mean ------2.824 -4.954 -7.003 Std.Dev. I.delta ------- ------0.055 0.053 0.050 -2.130 -2.049 Comments ------------------

Calibr. -------std.add.

Y.reg/offset ------------2.837e-009

Slope -----------2.305e-003

Std.Dev. -----------5.214e-011 Comments ------------------

Final results ---------------------------------Ti: Titanium = 1.353 g/L

+/- Res. dev. % -----------------0.035 2.554

Fig. 1 Titanium determination in seawater with the 757 VA Computrace

Application Bulletin Determination of titanium and uranium by voltammetry

No. 266/1 e Page 5

================== METROHM 746 VA TRACE ANALYZER (5.746.0101) ================== Method: AB266_1 .mth OPERATION SEQUENCE Title : Determination of Titanium. AB266 Method 1 -------------------------------------------------------------------------------Instructions t/s ------------- ----SMPL>M DOS>M PURGE STIR 30.0 (ADD PURGE STIR 10.0 0PURGE (REP SEGMENT REP)2 PURGE ADD>M ADD)1 END Main parameters ------------------------V.fraction mL Soln.name mandelic Rot.speed Rot.speed Segm.name Soln.name 2000 /min 2000 /min Ti_AdSV Ti_Std V.add 0.010 mL Auxiliary parameters ------------------------V.total L V.add 1.000 mL

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

SEGMENT Ti_AdSV -------------------------------------------------------------------------------Instructions t/s ------------- ----STIR 5.0 HMDE DPMODE MEAS 0STIR SWEEP 0MEAS END 30.0 5.0 19.6 Main parameters ------------------------Rot.speed 2000 /min Drop size 4 U.ampl -50 mV t.step 0.20 s U.meas -570 mV U.start U.end U.standby -570 mV -950 mV mV Auxiliary parameters ------------------------Meas.cell t.meas t.pulse U.step Sweep rate normal 20.0 ms 40.0 ms 4 mV 20 mV/s

Method: AB266_1

1 2 3 4 5 6 7 8

Fig. 2 Parameters for the determination of titanium with the 746 VA Trace Analyzer

Method 2 Uranium determination

Theory
Uranium forms a complex with chloranilic acid which can be determined by adsorptive stripping voltammetry.

Reagents
All of the used reagents must be of purest quality possible (analytical grade or suprapur). Only ultrapure water should be used. Chloranilic acid (2,5- dichloro-3,6-dihydro-1,4-benzoquinone), puriss p.a. CAS 87-88-7 Sulfuric acid, suprapur, w(H2SO4) = 96 % Sodium hydroxide solution, suprapur, w(NaOH) = 30 % U standard stock solution, (U) = 1 g/L (commercially available)

Application Bulletin Determination of titanium and uranium by voltammetry

Ready-to-use solutions CAA solution: c(chloranilic acid) = 510 mol/L 0.104 g chloranilic acid are dissolved in 100 mL ultrapure water.
-3

No. 266/1 e Page 6

diluted sulfuric acid: c(H2SO4) = 1 mol/L Sulfuric acid is diluted with ultrapure water as appropriate. U standard solution: (U) = 1 mg/L The standard stock solution is diluted with c(H2SO4) = 0.002 mol/L.

Analysis
Measuring solution 10 mL (diluted) sample + 0.1 mL CAA solution Adjust the pH value to 2.5 0.1 with w(NaOH) = 30 % or c(H2SO4) = 1 mol/L. The voltammogram is recorded with the following parameters:
Working electrode Stirrer/RDE Drop size Measurement mode Purge time Pulse amplitude Deposition potential Deposition time Equilibration time Start potential End potential Voltage step Voltage step time Sweep rate Peak potential (U) HMDE 2000 7 DP 300 s 0.05 V - 0.04 V 15 s 5s - 0.04 V - 0.3 V 0.004 V 0.1 s 0.04 V/s - 0.11 V

The concentration is determined by standard addition.

Remarks
The uranium concentration in the vessel should not exceed 500 ng absolute (with standard additions). If concentrations are higher, either the sample must be diluted or the analysis must be done at the SMDE. Higher uranium concentrations also require more CAA. Mo, Sb, Sn and V form CAA complexes as well. These do not interfere with the determination, do, however, perhaps require more CAA solution.

Application Bulletin Determination of titanium and uranium by voltammetry Figures

No. 266/1 e Page 7

I (nA)

I (nA) -70 -60 -50 -40 -30 -20 -10 -80 -100 -120 -140 -160 -180 U (mV)

-80 -70 -60

-50 -40 -30 -20

-10 0 5 10 15 20 25 30 35 rho(eff) (g/L)

================== METROHM 746 VA TRACE ANALYZER (5.746.0101) ================== Determ. : 06091533 User: zu Date: 1998-06-09 Modified : no Run : 0 Time: 15:33:20 Sample table: -------------------------------------------------------------------------------Pos. Ident.1/S1 Ident.2/S2 Ident.3/S3 Method.call Sample size/S0 Seawater pH2.47 50 uL -------------------------------------------------------------------------------Method : U_AdSV Title : Determination of Uranium Remark1 : 50 uL seawater + 9.95 mL H2O + 0.1 mL CAA solution -> pH 2.47 Remark2 : -------------------------------------------------------------------------------Substance : Uranium Mass conc.: 3.179 mg/L MC.dev. : 0.092 mg/L (2.91%) Cal.dev. : VR --00 01 02 10 11 12 20 21 22 Substance --------Uranium U/mV -----110 -110 -110 -109 -109 -109 -108 -109 -109 I/nA ------32.51 -32.35 -32.74 -51.53 -52.93 -53.13 -70.72 -72.81 -72.68 Mass : 158.9 ng Add.mass : 100 ng V0.sample: 50 uL Std.dev. I.delta ------- ------0.1934 0.8722 1.173 -19.99 -19.54 Comments ------------------

I.mean ------32.53 -52.53 -72.07

Comments ------------------

Techn. -------std.add.

Y.reg/offset ------------3.255e-08

Slope ----------0.002078

Nonlin. ----------

Mean deviat. -----------7.961e-10

Final results --------------------------------Uranium = 3.1788 mg/L

+/- Res.dev. % ----------------0.092 2.91

Comments ------------------

Fig. 3 Uranium determination with the 746 VA Trace Analyzer

Application Bulletin Determination of titanium and uranium by voltammetry

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================== METROHM 746 VA TRACE ANALYZER (5.746.0101) ================== Method: AB266_2 .mth OPERATION SEQUENCE Title : Determination of Uranium. AB266 Method 2 -------------------------------------------------------------------------------Instructions t/s ------------- ----SMPL>M DOS>M PURGE STIR 300.0 (ADD PURGE STIR 20.0 0PURGE (REP SEGMENT REP)1 PURGE ADD>M ADD)2 END Main parameters ------------------------V.fraction mL Soln.name CAA_sol Rot.speed Rot.speed Segm.name Soln.name 2000 /min 2000 /min U_AdSV U_Std V.add 0.100 mL Auxiliary parameters ------------------------V.total L V.add 0.100 mL

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

SEGMENT U_AdSV -------------------------------------------------------------------------------Instructions t/s ------------- ----STIR 5.0 HMDE DPMODE MEAS 0STIR SWEEP 0MEAS END 15.0 5.0 6.9 Main parameters ------------------------Rot.speed 2000 /min Drop size 7 U.ampl -50 mV t.step 0.10 s U.meas -40 mV U.start U.end U.standby -40 mV -300 mV mV Auxiliary parameters ------------------------Meas.cell t.meas t.pulse U.step Sweep rate normal 20.0 ms 40.0 ms 4 mV 40 mV/s

Method: AB266_2

1 2 3 4 5 6 7 8

Fig. 4 Parameters for the determination of uranium with the 746 VA Trace Analyzer